Vat dyestuffs of the anthraquinone series



Patented Jani 27, 1931 U ITED stares IvIAXnLBERT Kunz AND FREIHERB- sumo-ton RosEiIBnRG, OF. MANNHEIMQHAND EDUARDGOFFERJE, 0F FRANKsos'r a ren- AIN; GERMANY, ASSIGNORS T0 GEN- f ERALANILINE WORKS, INC on NE -YoRK;-N. 'Y., A' CORPORATION OF DELAWARE vsT nY s'rUsFs on THE ANTI-IRAQUINONE snalns No Drawing. Application fi ledAu gust is, 1927, Serial No. 212,844, andineermn August is, 1926.

he present invention relates to; new anthraquinone-ozzazoles, more particularly to compounds of the general formula one radical and wherein both anthraqui-n one nuclei may be substituted or not.

The new compounds are obtainable in a,

great variety of ways, For example they are formed when amino-anthraqu1nones which contain a negative substituent'such as a hydroXyl-group or a halogen atom in o-p-osition to the amino-group, are condensed with anthraquinone-aldehydes in the presence or absence of solvents and preferably at an elevated temperature. Instead of anthraquinone-aldehydes we 'mayuse other anthraquinone derivatives with aldehyde properties for instance anthraquinone-isoxazoles,'

or anthraquinone-carboxylic acids or compounds reactmg like them suchas the'ac d halides, esters and similarly acting compounds. V I p 7 The new products may also be obtained by condensing anthraquinones contannng two negative substituents. in o-position to each other with anthraquinone-carboxylic acid amids. A modification-0t the said wayot preparing the new anthraquinone-oxazoles consists in condensing anthraquinonecarbonylamino-anthraquinones which are substituted by hydroxyl groups or other negative substituents in the o-po-sition to the amino group; the sa d anthraqulnone-carbonylamino-anthraquinones may be obtained in a very advantageous manner by condensing an anthraquinone-carboxylic acid halide with an amino-anthraquinone containing a hydroxyl group or othernegative substituent in o-position to the amino group, but they may also he of the anthraquinone radicles. The products dissolve in concentrated sulfuric acidin most cases with the formation ot yellow to orange solutions.

.Those products which may. be. derived from 2.3 amino hydroXy-, 1.2 amino-hydroxyand 2.1,-amino-hydroxy-anthraquinone and contain an amino group in the 1-positi0n' of the anthraquinone radical actmg as a substituent in the -positionot the oxazole nucleus-, especially those which correspond to the formula and respectively, are of particular value; they dye practically the same shades oi excellent tastness and-arealso very valuableintermediate products for the production, of ne w, dyestuffs. I I. m

WVe have further found that, by the action of fuming sulfuric acid on such dyestuffs I produced as hereinbefore described, as contain at least one treeannno grou in alphapositlon in one or both of the ant iraquinone radicals, products of considerable deeper color are obtained. The action of the fuming sulfuric acid may be considerably. ac-

- fibres from, the alkaline hydrosulphite vat.

celerated by additions such as sulfur or iodine, and the concentration of the fuming sulfuric acid and the reaction temperature, may be varied within wide limits. It is prob} able that in this treatment no sulfonation 'or condensation takes place but that a hydroxyl 7. group is formed in the para-position to the J amino group ;v accordinglythe productiobtained for example from the dyestufi' of the formula v i r N112 o' r c U o l/(lk I V MOLD is considered to correspond to the formula The said new products furnish violet to blue dyeings of excellent fastness on vegetable They are not soluble in, and their shades are not altered by aqueous alkalis. They dissolve in concentrated sulfuric acid in most tinctorial properties are obtained. I

alkyl ethers are rather similar in their propcases with an orange coloration.

On treating these new dyestuffs contain ing hydroxyl groups with alkylating agents,

as for example with p-toluene-sulfonic acid methyl ester, the hydroxyl group is etherified and other new dyestuffs'with excellent These cities to the aforesaid compounds with free hydroxyl groups. Their shades are in most cases more violet and their fastness to ch10 rine 1s still better.

Those anthraquinone-oxazoles which have I been mentioned above as being of particular value, are best suitable alsofor the treatment with fuming sulfuric acid with or without subsequent alkylation.

The following examples will further illustrate the nature of the said invention which however is not limited thereto. The parts are by weight.

Example 1 5 parts of 2.3-amino-hydroxy-anthraquinone obt ainable by i treating 2.3-bromhydroxy-anthraqui'none with concentrated: ammonia at 130 for 5 hours-are intimately mixed with"? parts of anth'ra quinone-Q-aldhyde, and heated for example for 1 hours at-25O CE-until a sample no longer gives the color reaction of 2.3-am1no-hydroxy-anthraing to the formula quinone with alkalisj After cooling,- the greyish-brown reaction product correspond- H i E N V l i i l I i is crushed and is purified by recrystallization from nitrobenzene. It is then in the form of yellow crystals, which dissolve to a reddishbrown solution in sulfuric acid. The hydroline)-in 25- parts of nitrobenzene until unaltered Q-amino l-hydroxyanthra-quinone can no longer be detected. The reaction proceeds according to the following equation:

Iv-c6115 NHzf) v ,l n i i +HzN-com+m,

V I? OAOMQ- l I the hydrogen formed being consmned by reduction of" the v nitrobenzei e. After cooling,

the dyestuff which has separated out as brownisli-red necdles with avcopp ery lustre, is filtered by suction and washed with nitrobenzene until i the washing liquid exhibits merely a slight tinge. The nearly puredyestuff which corresponds to the formula may be further purified by recrystallization from nitrobenzene, and then dissolves to a yellow solutionin sulfuric acid; from which solution it is thrown down by water in the 7 form of red flakes with a bluishtinge. It-

gives deep cherry red dyeings on cotton, from a vat of the same color. -Oxidation changes the shade tinge.

to a very fast red with a bluish E mample 3, i

3 parts of 3-arnino-alizarine and 4 parts of l-annno-anthraqulnoneQ-aldehyde are heat ed in 40 parts .of boiling nitroloenzene until 7. the reaction mixture no longercontains any detectable amount of matter which is soluble in alkali. After, cooling, the solid product is filtered by suction and washed with nitrobenzene until the washing liquid shows mere-f 1y a slight tinge. The residue is a reddishbrown dyestuff which corresponds tothe formula 1 and dissolves to an orange solution in sulfuric acid: and is precipitated therefrom by water in the form of'b'rownish-red flakes,

the color of which changes to violet under the action of alkali. If the dyestuff be allrylated,

for exam le b treatin the same in soluo u o o tlon or suspension in o-dichlorbenzene, with p-toluene-sulfonic acid methyl ester, a red product is'obtained which is fast to alkali,

di solves to an orange solution in sulfuric acid (from which it is precipitated in they form of red flakesby water) and gives dark colored dyeings on cotton from a deep violet vat (with an olive tinge), the'color changing, on oxidation to a powerful and very fast red.

Ewample 4 filtered by suction and can be further puri fied by recrystallization from intro-benzene, separating out in theform of reddish-brown crystals which correspond to the formula and dissolve to an olive solution in sulfuric acid. The dyeings on cotton from the red hydrosulphite'vat (with a violet tingelaie; of tlnslatter color, which changes, on oxi'da-I tio'n to a very fast,blue-tinged red.

. Example 5; r

3 parts of, the condensation product from 1.3-d1bro1n-2-aminoanthraqumone with an- -thraquinoneQ-carboxylic acid chlorid, of the j formula i are trit urated with 5 parts of naphthalene and 2 parts of calcined soda,'and are heated toboilingfor several hours, the mixture be- 111g kept stirred. 'lheresulting melt is freed from naphthalene by extraction with ben- "Zene, sodium'broinide and carbonate are .e:-;-

tracted with water. The. residual product may be furtherpurified by recrystallization, for exa r'nple from nitrobenzene. Yellow crystals corresponding probably to the formula are obtained which dissolve to a yellow soiut1on1n sulfuric acid. The violet-brown vat dyesWell on cotton, the color changing 'to light yellow on oxidation.

Ema mph (I 1 part'of the condensation product from 2.3-brom-a1nino anthra quinone and l.:2-a nino-antl1ra.quinone-carboxylic acid chloride of the formula:

, is stirred and heated to boiling, while stir ring, with 1.5 parts of naphthalene, 0.5 part of calcined soda, 0.01 part of copper acetate and 0.01 part of copper-bronze, until halogen can no longer be detectet in a saniple of the product boiled with alcohol'and wa er. The melt; is treated as described in Example mula The dyestuiilwhich corresponds to the fori may be further purified by recrystallization from solvents of high boiling point,'and it then dissolves to an olive-browii solution in sulfuric acid. Cotton is dyed a deep olive black in the vat the col-or changing, on oxidation, to anexceedingly fast red with bluish tinge.

Example '7,

10 parts of anthraiquinone-l.Q-isoxazole and 9 parts of 2.3-amino hy droxy anthraquinone are heated toboiling with 150 parts of Hi5 chlorbenzene until unaltered initial material can no longer be detected. The resu ting dvestuif is filtered by suction after cooling. The resulting dyestuff is filtered by suction after cooling. It can be purified by recrystallization from nitrobenzene; and is identical with the product described in Example 6.

Ewample 8 droXy-anthraquinone, the mixture is then slowly heated to the boil, and after a, further addition of 2 parts of para-toluene-sulfonic acid kept boiling, until a test-portion of the reaction product no longer shows a change in color on the addition of alkali. The dyestuff is then filtered off, While hot, by suction and washed withnitrobenzene. It is identical with the product described in Enample 6. V r

Emample 1 part of the dyestufl obtainedin the above described manner from 2.3-amino-hydroxyanthraquinone and 1-amino-anthraquinone- .Z-aldehyde is stirred into 10 parts-of fuming sulfuric acid (containing per cent-of anhydride) andJis left for about 50 hours at room temperature until the dyestuff, precipitated from a sample byice, separates out in 4 the form of pure blue flakes, and no further change is effected by the continuanceof the treatment. The solution-after dilution with sulfuric acid mono-hydrate if necessary-is then stirredinto' ice, the dyestuff being filtered by suction and washed until neutral. It can be completely purified-byre crystallization from organic solvents of high boiling point, in Which itdissolves to a blue solution. The product corresponds probably to the formula Its solution in concentrated sulfuric acid is orange-yellow in color. r

The dyeings from the blackish-violet vat are dark in color, changing to blue on oxidation.

In order to methylate' the dyestuff, 1 part thereof, is suspended in 20 parts of o-dichlorbenzene and is boiled and stirredvv'ith 1 part of p-toluene-sulfonic acid methyl ester and 1 part of carbonate ofpotash until the initially blue solution has become violet and no. further change of shade occurs. After coolmg. filtering by suctlonand washing with alcohol and then with Water, a violet prode not is left, which can be recrystallized from solvents of high boiling point and dissolves to an orange solution in concentrated sulfuric acid. The dyeings from the brownish-red vat change to an exceedingly fast violet on oxidation. I

Example. 10

1 part of the dyestuff obtainable according toEXample 4 is stirred into 8 parts of fummg sulfuric acid containing 50'percent of anhydride. After adding 01' part of iodine,"

the solution is left to standat room tempera.- ture until a sample deposits blue flakes on precipitation With ice. The further treatment is the same asin Example 9.

The dyestuff disolves to an orange solution in concentrated sulfuric acid. The dyeings from the violet vat turn blue on oxidation. A violet dyestuif is obtained by methylating as in Example 9.

Example 11" 1 partof the dyestuif'prepared in the aforedescribed manner from 1 molecular proportion of o-diamino-anthraflavic acid (obtainable by nitrating anthraflavic acid and reduction) and 2 molecular proportions of 1-amino-2anthraquinohe-aldehyde, which furnishes red dyeings with a bluish tinge,

is stirred at 50 (lwith 10 parts offuming sulfuric acid containing 65'per cent of anhydride, and 0.1 part of sulfur, until a sample gives a precipitate of dark blue flakes on addition of ice. The further treatment is the same as in Example 9. A dark blue-product anddissolves to an orange-brown solution in dyeings from the dark vat becomes darkblue is obtained which is considered to correspond lo the formula V El) NH: O

O OH

not.

I 2. As new articles of manufacture, anthraquinone-oxazoles derived from an anthraquinone derivative selected from'the group consisting of 2.3-amino-hydroxy-, 1Q2-aminohydroxyand 2.1-amino-hydroxy-anthraquinone, and containing another anthraquinone radicle as a substituent attached in its ,8-position to the ,a-position ofthe oxazole ring, which products correspond to the general formula V wherein C and C belong to an anthraquinone nucleus and wherein both anthraquinone nuclei may be substituted or not.

3. As new articles of mamifacture, anthraquinone-oxazoles derived from an anthraquinone derivative selected from the-group consisting of 2.3-amiuo-hydroXy-, 1.2-aminohydroxyand 2.1-amino-hydroxy-anthra quinone, and containing another anthraquinone radicleas a substituent in the ,u-position of the oxazole ring, which products correspond to the general formula:

wherein A indicates another anthraquinone radical and wherein atleastone of the thraqulnone nuclei conta ns anam no. group 1n alpha-posltlon audboth anthraquinone 7 nuclei may be further substituted or not.

4. As new arti'cle's of manufacture, vat

' dyestuffs which dye cotton fastviolet to blue 'shadesand are considered tocorrespond to I the generalformula whereinCyand cgbelong to" an anthraquinonenucleus and A indicatesfanother' anthraiquinone radical and wherein at 'least one of the anthraquinone nuclei containsfan 7 amino group in alph'a position and an ,group in para positi'on thereto, R indicating hydrogen orv an al'kyl group, both anthraquinonenuclei being furthersubstituted or .not. i

5. As new articles A of manufacture, .vat dyestuffs which dye cotton fast violet to blue shades and are considered; to correspond to the general formula" quinone nucleus containing Ianother anthraquinone radicle as a substituent attached in its ,B-position' to'the 'u-position' of the oXazo-le wherein Grand C belong to an" anthraring and wherein at least one of theanthra quinone nuclei contains an amino group in alpha-position'and an ()R group in paraposition thereto, R indicating hydrogen or an alkyl group, both anthraquinone nuclei being further substituted or not.-

6. As new articles of manufacture, vat

, dyestuffs which dye cotton fast violet to blue shades ancLare considered to correspond to the general formula i I N112 '0 quinone nucleus and containing an ri -amino anthraquinone radicle attached in the orthoposition to the amino group to the it-position of the oxazole ring and substituted in the para-position to the amino group by the O-R group in which R indicates hydrogen I or an alkyl group.

7. As new articlesof manufacture, vat

c '120 wherein C and C belong to an anthradyestuffs which are conside ed to correspond to the general formula wherein C and C belong to an anthraquinone nucleus. I

8. As new articles of manufacture, anthraiquinoneo xazoles derived from an enthraquinoneIdei-ivative selected from the group epnsisting of 2.3-aming-hydr0xy-5-1.2 a.min0r quinone which products EUL'G considered to eer 'esp'oncl to the general formula,

wherein C and C belong to an anthraquinone nucleus and contain the alphaaininoanthraquinone radicle attached in the ortho-positien to the amino group to the ,wposition of the oxazole ring,- and wherein both anthr z quinone nuclei maybe further substituted. V r V In testimony whereof We havehereunto set ourhands.

" AX ALBERT KUNJZI' FREKHERRY sumo v fkosmseae.

EDUARD GOFF JEQ" 

